CN105206774A - Battery - Google Patents

Battery Download PDF

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Publication number
CN105206774A
CN105206774A CN201510536774.0A CN201510536774A CN105206774A CN 105206774 A CN105206774 A CN 105206774A CN 201510536774 A CN201510536774 A CN 201510536774A CN 105206774 A CN105206774 A CN 105206774A
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CN
China
Prior art keywords
carrier ring
coating
active material
insulating properties
tackifier
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Granted
Application number
CN201510536774.0A
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Chinese (zh)
Other versions
CN105206774B (en
Inventor
大钟真吾
梅原将一
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Toyota Motor Corp
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Toyota Motor Corp
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Filing date
Publication date
Application filed by Toyota Motor Corp filed Critical Toyota Motor Corp
Priority to CN201510536774.0A priority Critical patent/CN105206774B/en
Priority claimed from CN201080070322.3A external-priority patent/CN103229341B/en
Publication of CN105206774A publication Critical patent/CN105206774A/en
Application granted granted Critical
Publication of CN105206774B publication Critical patent/CN105206774B/en
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Classifications

    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/403—Manufacturing processes of separators, membranes or diaphragms
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/409—Separators, membranes or diaphragms characterised by the material
    • H01M50/411—Organic material
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M50/00—Constructional details or processes of manufacture of the non-active parts of electrochemical cells other than fuel cells, e.g. hybrid cells
    • H01M50/40—Separators; Membranes; Diaphragms; Spacing elements inside cells
    • H01M50/46—Separators, membranes or diaphragms characterised by their combination with electrodes
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/052—Li-accumulators
    • H01M10/0525—Rocking-chair batteries, i.e. batteries with lithium insertion or intercalation in both electrodes; Lithium-ion batteries
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M10/00—Secondary cells; Manufacture thereof
    • H01M10/05—Accumulators with non-aqueous electrolyte
    • H01M10/058—Construction or manufacture
    • H01M10/0587—Construction or manufacture of accumulators having only wound construction elements, i.e. wound positive electrodes, wound negative electrodes and wound separators
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/20—Batteries in motive systems, e.g. vehicle, ship, plane
    • H—ELECTRICITY
    • H01—ELECTRIC ELEMENTS
    • H01M—PROCESSES OR MEANS, e.g. BATTERIES, FOR THE DIRECT CONVERSION OF CHEMICAL ENERGY INTO ELECTRICAL ENERGY
    • H01M2220/00—Batteries for particular applications
    • H01M2220/30—Batteries in portable systems, e.g. mobile phone, laptop
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02E—REDUCTION OF GREENHOUSE GAS [GHG] EMISSIONS, RELATED TO ENERGY GENERATION, TRANSMISSION OR DISTRIBUTION
    • Y02E60/00—Enabling technologies; Technologies with a potential or indirect contribution to GHG emissions mitigation
    • Y02E60/10—Energy storage using batteries
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
    • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
    • Y02P70/00—Climate change mitigation technologies in the production process for final industrial or consumer products
    • Y02P70/50—Manufacturing or production processes characterised by the final manufactured product

Abstract

The invention provides a battery which comprises a positive pole, a negative pole and a partition board layer. The positive pole is provided with a positive pole current collector and a positive pole active substance layer which contains positive pole active substances and is formed on the positive pole current collector. The negative pole is provided with a negative pole current collector and a negative pole active substance layer which contains negative pole active substances and is formed on the negative pole current collector. The partition board layer contains insulating particles, an adhesive and a tackifier, is formed on the surface of at least one of the positive pole active substance layer and the negative pole active substance layer, and has insulativity and porosity. The mass proportion of the adhesive in the partition board layer is smaller than 2%, and the mass proportion of the tackifier in the partition board layer is 0.2-22.6%.

Description

Battery
The divisional application that the application is the applying date is on November 24th, 2010, application number is 201080070322.3, name is called the patent application of " manufacture method of battery and battery ".
Technical field
The present invention relates to the manufacture method of battery and battery.
Background technology
All the time, as the electrode body of battery, normal use possesses the electrode body of positive pole, negative pole and the dividing plate between positive pole and negative pole.Such as, the electrode body of the lithium ion battery improved paid close attention in recent years by the drive source as electronic equipment, vehicle, often makes the positive pole of sheet, negative pole and dividing plate carry out the electrode body reeled that overlaps.According to this battery, the surface area of the per unit volume of positive pole and negative pole can be increased, the raising of energy density can be sought.
In addition, in order to improve the battery performance of so-called high-rate characteristics etc., expect the efficiency of the ionic conduction between positive pole and negative pole is further improved.When the efficiency of ionic conduction improves, the ion permeability improving dividing plate is effective, therefore expects that the thickness of dividing plate is little, and the flatness on surface is high.
All the time, as dividing plate, often use the resin film of the polyolefin of polyethylene, polypropylene etc.But the dividing plate of resin film, needs mechanical strength to a certain degree, makes not rupture when the assembling of battery.Therefore, the dividing plate of resin film, from the viewpoint of strength maintenance, thickness thinning compared with the past is more difficult.
Therefore, the scheme (for example, referring to patent documentation 1 and 2) of the layer, the i.e. carrier ring that directly form the function playing dividing plate on the surface of positive pole or negative pole is proposed.In patent documentation 1 and 2, record following method, by the coating of modulation containing insulating properties particle, adhesive and solvent, and by making it dry after this coatings to the surface of the active material layer of negative or positive electrode, form carrier ring on the surface of negative or positive electrode.
At first technical literature
Patent documentation 1: No. 97/08763rd, International Publication
Patent documentation 2: Japanese Patent Application Publication 2000-149906 publication
Summary of the invention
The present application person, has found when the method as described above of employing defines carrier ring on the surface of negative or positive electrode, is formed large concavo-convex, according to circumstances produce pin hole (pinhole) on the surface of carrier ring.But, if the flatness on the surface of carrier ring is low, then there is the distance between the surface of positive pole and the surface of negative pole (so-called anode-cathode distance) to produce deviation, battery performance occurs the anxiety of deviation.In addition, if the flatness on the surface of carrier ring is low, then there is the anxiety of the insulating properties reduction of carrier ring.
The object of this invention is to provide a kind of battery being formed with carrier ring on the surface of at least one party of positive pole and negative pole, the flatness on the surface of the carrier ring of this battery is high.Another object of the present invention is to provide a kind of manufacture method manufacturing this battery.
According to the present invention, there is provided a kind of manufacture method of battery, this battery possesses: the positive pole with positive electrode active material layer, the negative pole with negative electrode active material layer and the carrier ring formed on the surface of at least one party of positive electrode active material layer and negative electrode active material layer.The manufacture method of the battery that the present invention relates to, it comprises: the operation preparing positive pole, and this is just having positive electrode collector and is containing positive active material and the positive electrode active material layer formed on above-mentioned positive electrode collector; Prepare the operation of negative pole, this negative pole has negative electrode collector and contains negative electrode active material and the negative electrode active material layer formed on above-mentioned negative electrode collector; Make the operation of coating, this operation at least makes insulating properties particle, adhesive and solvent mix, and makes the coating that viscosity is the carrier ring formation of 500mPas ~ 5000mPas; With by being coated with above-mentioned coating and making it dry on the surface of at least one party of above-mentioned positive electrode active material layer and above-mentioned negative electrode active material layer, form the operation with insulating properties and porous carrier ring.
The present application person thinks, one of reason that the flatness as carrier ring reduces, has reason as described below.That is, by the coatings that comprises insulating properties particle, adhesive and solvent when active material layer surperficial of negative or positive electrode, this solvent infiltrates in active material layer, and air is extruded from active material layer.This air, passes through, after arriving the surface of film, is discharged into outside in the film of coating forming carrier ring.Think now, this air is formed concavo-convex on the surface of film.
According to the manufacture method that the present invention relates to, the coating that carrier ring is formed, its viscosity is adjusted to more than 500mPas.Because the ratio of viscosities of coating is comparatively large, so solvent can be suppressed to infiltrate in active material layer.Therefore, the amount of the air extruded from active material layer reduces, and can improve the flatness of carrier ring.But when the viscosity of coating is excessive, the coating weight of coating becomes easily has deviation.According to the manufacture method that the present invention relates to, the viscosity of coating is adjusted to below 5000mPas.Therefore, the deviation of coating weight can be suppressed.
In the preferred mode of manufacture method of battery disclosed herein, in the operation of above-mentioned making coating, relative to insulating properties particle 100 weight portion, also add the tackifier of 0.5 weight portion ~ 65 weight portion.In another preferred mode of the manufacture method of battery disclosed herein, in the operation of above-mentioned making coating, the use level of above-mentioned adhesive is below 3 weight portions relative to insulating properties particle 100 weight portion.In another preferred mode of the manufacture method of battery disclosed herein, in the operation of above-mentioned making coating, the use level of above-mentioned adhesive, be below 3 weight portions relative to insulating properties particle 100 weight portion, relative to insulating properties particle 100 weight portion, also add the tackifier of 0.5 weight portion ~ 65 weight portion.Thus, the viscosity of coating is modulated to suitable scope and becomes easy.
In the preferred mode of battery disclosed herein, the average grain diameter of above-mentioned insulating properties particle is more than 3 μm, and the porosity of aforementioned barriers layer is more than 35%.Thus, can obtain that there is the carrier ring with in the past equal ion permeability.
Accompanying drawing explanation
Fig. 1 is the sectional view of the electrode body representing the battery that an execution mode relates to.
Fig. 2 is the sectional view of the electrode body representing the battery that another execution mode relates to.
Fig. 3 is the sectional view of the electrode body representing the battery that another execution mode relates to.
Fig. 4 is the stereogram of the Inner Constitution representing the battery that an execution mode relates to.
Fig. 5 is the side view representing the vehicle (automobile) possessing the battery that an execution mode relates to.
Fig. 6 is the figure of the relation representing the weight ratio of adhesive and the viscosity of coating.
Fig. 7 is the figure of the relation representing the weight ratio of tackifier and the viscosity of coating.
Fig. 8 is the figure of the relation representing the weight ratio of tackifier and the viscosity of coating.
Fig. 9 is the sectional view representing the formation measuring the sample used in the experiment of the venting quality of carrier ring.
Figure 10 is the figure of the relation representing the average grain diameter of insulating properties particle and the porosity of carrier ring.
Embodiment
Below, illustrate preferred embodiment of the present invention.Moreover the necessary matters of beyond the item mentioned especially in this manual, of the present invention enforcement, can based on the prior art in this field, and the design item as those skilled in the art is grasped.The present invention can implement based on the technology general knowledge in the content disclosed in this specification and this field.
Technology disclosed herein, can be widely used in the manufacture of following battery and this battery, this battery possesses: the positive pole of positive electrode active material layer having positive electrode collector and formed on above-mentioned positive electrode collector; The negative pole of the negative electrode active material layer that there is negative electrode collector and formed on above-mentioned negative electrode collector; And formed on the surface of at least one party of above-mentioned positive electrode active material layer and above-mentioned negative electrode active material layer, between above-mentioned positive electrode active material layer and above-mentioned negative electrode active material layer, there is insulating properties and porous carrier ring.Battery disclosed herein can be primary cell, also can be secondary cell.Below, mainly in further detail the present invention is described for lithium rechargeable battery, but is not intended applicable object of the present invention to be defined in this battery.
As shown in Figure 1, lithium rechargeable battery of the present embodiment, possesses the electrode body 1 with positive pole 10 and negative pole 20.Positive pole 10, have sheet positive electrode collector 11 and containing positive active material and on positive electrode collector 11 formed positive electrode active material layer 12.Negative pole 20, has the negative electrode collector 21 of sheet and contains negative electrode active material and the negative electrode active material layer 22 formed on negative electrode collector 21.Moreover the shape of positive pole 10 and negative pole 20 is not limited to sheet, also can be bar-shaped other shapes such as grade.
On the surface of positive electrode active material layer 12, be formed and there is insulating properties and porous carrier ring 30.In FIG, positive pole 10 and negative pole 20 are illustrated discretely, but in fact positive pole 10 and negative pole 20 overlap.Carrier ring 30, between positive pole 10 and negative pole 20, in more detail between positive electrode active material layer 12 and negative electrode active material layer 22.Between positive pole 10 and negative pole 20, ion conduction pathway is formed by the hole in carrier ring 30.Moreover, carrier ring 30 between positive pole 10 and negative pole 20, the configuration mode of carrier ring 30 without particular limitation of.As shown in Figure 1, carrier ring 30 can be formed on the face of a side of the face of a side of positive pole 10 and negative pole 20.In addition, as shown in Figure 2, carrier ring 30 also can be formed on the two sides of positive pole 10.In this situation, because become carrier ring 30 between positive pole 10 and negative pole 20, so not necessarily need to arrange carrier ring 30 on the surface of negative pole 20.As shown in Figure 3, also carrier ring 30 can be formed on the two sides of negative pole 20.In this situation, not necessarily need to arrange carrier ring 30 on the surface of positive pole 10.But, also can form carrier ring 30 respectively on the surface of the surface of positive pole 10 and negative pole 20, and these carrier rings 30 are configured with overlapping.
In Fig. 1 etc., illustrate only each positive pole 10 and negative pole 20, but positive pole 10 and negative pole 20 also can differently from each other stacked many pieces.In addition, positive pole 10 and negative pole 20 also can reel under the state overlapped.
First, carrier ring 30 is described.Carrier ring 30 has insulating properties and porousness.In addition, carrier ring 30 has thermoplasticity, if become more than set point of temperature, melting, inner hole is blocked.Namely carrier ring 30 has so-called closedown (shutdown) function.
Carrier ring 30, is coated on the surface of positive electrode active material layer 12 or the surface of negative electrode active material layer 22 by the composition (hereinafter referred to as coating) formed by carrier ring, and this coating drying is formed.The viscosity of coating, is preferably 500mPas ~ 5000mPas.Moreover the viscosity of the coating in this specification is the viscosity utilizing the Brookfield viscometer that rotating speed is 60rpm to determine.Coating comprises insulating properties particle, the adhesive bondd by insulating properties particle and makes the solvent of insulating properties particle and adhesive dispersion, also suitably comprises tackifier.By the carrier ring 30 making above-mentioned coating drying be formed, containing insulating properties particle and adhesive, also suitably containing tackifier.
Though the thickness of carrier ring 30 is without any restriction, is preferably such as 1 μm ~ 100 μm, is more preferably 10 μm ~ 50 μm.The thickness hour of carrier ring 30, has the tendency that the insulating properties between positive pole 10 and negative pole 20 reduces.On the contrary, when the thickness of carrier ring 30 is excessive, the ratio of carrier ring 30 shared by electrode body 1 becomes large, has the tendency causing battery capacity to reduce.
Though the porosity of carrier ring 30 is not particularly limited, the viewpoint of or ion permeability it more than equal from the dividing plate in the past kept with to be made up of polyethylene film etc., preferably more than 35%.The porosity of carrier ring 30, can calculate as described below.With the apparent volume shared by the carrier ring 30 with the surface area of unit are for V1 [cm 3].With the quality W [g] of above-mentioned carrier ring 30 and density (solid constituent density) ρ [g/cm of material being formed aforementioned barriers layer 30 3] ratio, W/ ρ be V0.Moreover the carrier ring that V0 is quality W forms the volume shared by DB of material.Now, the porosity of carrier ring 30, can be calculated by (V1-V0)/V1 × 100.
Insulating properties particle, can use the particle from the various materials used in the past.Insulating properties particle can be the particle of inorganic matter, also can be organic particle.As inorganic matter, can use such as, the slightly solubility ionic crystal particle etc. of the covalency key crystalline particle, barium sulfate, calcirm-fluoride, barium fluoride etc. of the nitride, silicon, diamond etc. of the oxide, aluminium nitride, boron nitride etc. of iron oxide, silica, aluminium oxide, titanium oxide etc.As organic substance, can use such as, polyethylene, polypropylene, polystyrene, polyvinyl chloride, polyvinylidene chloride, polyacrylonitrile, polymethyl methacrylate, polyacrylate, fluororesin (such as, polytetrafluoroethylene, polyvinylidene fluoride etc.), polyamide, polyimide resin, mylar, polycarbonate resin, polyphenylene oxide resin (polyphenyleneoxideresin), silicones, phenol resin, urea resin, melmac, polyurethane resin, polyether resin (such as, poly(ethylene oxide), PPOX etc.), epoxy resin, acetal resin, AS resin and ABS resin etc.
The average grain diameter of insulating properties particle, is preferably such as 0.1 μm ~ 10 μm, is more preferably 1 μm ~ 6 μm.The porosity of carrier ring 30 is set to the situation of more than 35%, the average grain diameter of insulating properties particle is preferably more than 3 μm.The shape of particle is not limited to spherical, also can be needle-like, bar-shaped, other shapes such as fusiform, tabular.
Adhesive, can use the various materials from using in the past.As adhesive, various polymer, ionomer resin etc. can be used.As adhesive, also can use such as, latex (such as, Styrene-Butadiene latex, acrylonitrile-butadiene copolymer latex etc.), cellulose derivative (such as, the sodium salt etc. of carboxymethyl cellulose), fluorubber (such as, the copolymer etc. of vinylidene fluoride, hexafluoropropylene and tetrafluoroethene), fluororesin (such as, polyvinylidene fluoride, polytetrafluoroethylene etc.) etc.
The use level of the adhesive in coating is not particularly limited, but the use level of adhesive, also can be set to below 3 weight portions relative to insulating properties particle 100 weight portion.Thus, the viscosity of coating is adjusted to above-mentioned scope and becomes easy.
As described above, for adjusting the viscosity of coating, also tackifier can be added in coating.The material of tackifier is not particularly limited.Can be used in battery well and stably exist, not hinder the various tackifier of the original function of carrier ring 30.As tackifier, can use such as, Sodium Polyacrylate, ammonium polyacrylate etc.
The addition of tackifier, can suitably adjust to make the viscosity of coating to become 500mPas ~ 5000mPas.Such as, also the addition of tackifier can be set to 0.5 weight portion ~ 65 weight portion relative to insulating properties particle 100 weight portion.Thus, the viscosity of coating is adjusted to above-mentioned scope and becomes easy.
Then, positive pole 10 is described.Positive pole 10 can use certainly in the past as the various positive poles that the positive pole of lithium rechargeable battery uses.As positive electrode collector 11, component metal good for the conductivity of copper, nickel, aluminium, titanium, stainless steel etc. and so on being configured to main body can be used.As the positive electrode collector 11 of lithium rechargeable battery, can preferably use aluminium or take aluminium as the alloy (aluminium alloy) etc. of principal component.As other example, can enumerate zinc, tin etc. amphoteric metal and with any one alloy being principal component of these metals.The shape of positive electrode collector 11 is not particularly limited, but in the present embodiment, uses the positive electrode collector 11 of the aluminum of sheet.Such as, thickness can be used well to be the aluminium flake of 10 μm ~ about 30 μm.
As the positive active material of positive electrode active material layer 12, use can occlusion and release lithium material, can be not particularly limited to use one or more of the material (such as, the oxide of layer structure or the oxide of spinel structure) used from lithium rechargeable battery in the past.Can enumerate such as, the lithium-contained composite oxide of lithium-nickel-based compound oxide, lithium-cobalt system composite oxides, lithium manganese system complex oxide, lithium magnesium system complex oxide etc.
At this, so-called lithium-nickel-based compound oxide, refer to the following meaning: be the oxide being formed metallic element with lithium (Li) and nickel (Ni), to be also contained in addition beyond lithium and nickel also in atomicity convert using with nickel same degree or the ratio fewer than nickel (typically few than nickel ratio) containing other at least one metallic element (that is, the transition metal beyond Li and Ni and/or typical metal elements) as the oxide being formed metallic element.Metallic element beyond above-mentioned Li and Ni, can be such as, be selected from one or more the metallic element in cobalt (Co), aluminium (Al), manganese (Mn), chromium (Cr), iron (Fe), vanadium (V), magnesium (Mg), titanium (Ti), zirconium (Zr), niobium (Nb), molybdenum (Mo), tungsten (W), copper (Cu), zinc (Zn), gallium (Ga), indium (In), tin (Sn), lanthanum (La) and cerium (Ce).Moreover, be also the same meaning for lithium-cobalt system composite oxides, lithium manganese system complex oxide and lithium magnesium system complex oxide.
In addition, also general formula LiMPO can be used 4(M is the element of more than at least one among Co, Ni, Mn, Fe; Such as LiFePO 4, LiMnPO 4) the olivine-type lithium phosphate that marks is as positive active material.
As other example of positive active material adoptable in technology disclosed herein, the positive active material of the so-called polyanion system of LiFePO4, LiNiPO, cobalt phosphate lithium, lithium manganese phosphate, ferric metasilicate lithium etc. can be enumerated.
Positive electrode active material layer 12, except positive active material, can contain electric conducting material, adhesive etc. as required.As electric conducting material, the material with carbon element of carbon black (such as acetylene black), powdered graphite etc. preferably can be used in the same manner as the electric conducting material in the electrode of general lithium rechargeable battery.As adhesive, polyvinylidene fluoride (PVDF), carboxymethyl cellulose (CMC), styrene butadiene rubbers (SBR) etc. can be used.Though be not particularly limited, electric conducting material, relative to the use amount of positive active material 100 weight portion, can be set to such as 1 weight portion ~ 20 weight portion.In addition, adhesive, relative to the use amount of positive active material 100 weight portion, can be set to such as 0.5 weight portion ~ 10 weight portion.
Positive electrode active material layer 12, can such as make as follows.First, be produced in the liquid medium containing suitable solvent and adhesive and disperseed the composition of the form of positive active material and the electric conducting material composition of slurry (typically stick with paste or).Then, above-mentioned composition is coated on positive electrode collector 11 and makes it dry, suppress according to required.Thus, positive electrode active material layer 12 can be obtained.Moreover, as above-mentioned solvent, any one of water, organic solvent and their mixed solvent can be used.
Then, negative pole 20 is described.Negative pole 20, can be used as the various negative poles from the negative pole use of lithium rechargeable battery in the past.As negative electrode collector 21, preferably use the electroconductive member be made up of the metal that conductivity is good.Such as, copper can be used or take copper as the alloy of principal component.The shape of negative electrode collector 21 is not particularly limited, but in the present embodiment, uses the negative electrode collector made of copper 21 of sheet.Such as, thickness can be used well to be the copper sheet of 5 μm ~ about 30 μm.
As negative electrode active material, can be not particularly limited to use certainly one or more of the material of lithium rechargeable battery use in the past.Such as, carbon particle can be enumerated as suitable negative electrode active material.The emboliform material with carbon element (carbon particle) of preferred use at least partially containing graphite-structure (layer structure).Also can use the material (soft carbon) of the material (hard carbon) of the material of so-called graphite (graphite), difficult graphitization carbonaceous, easily graphitization carbonaceous well, there is any one material with carbon element of the material of the structure they be combined with.
Negative electrode active material layer 22, except negative electrode active material, can as required containing the electric conducting material, adhesive etc. same with positive electrode active material layer 12.Though be not particularly limited, adhesive, relative to the use amount of negative electrode active material 100 weight portion, can be set to such as 0.5 ~ 10 weight portion.Above-mentioned negative electrode active material layer 22, can by having disperseed the composition of the form of negative electrode active material in the liquid medium be produced on containing suitable solvent and adhesive same with positive electrode active material layer 12, said composition being coated on negative electrode collector 21 makes it dry, suppress according to required, make well.
As described above, carrier ring 30, makes its drying to be formed on the surface of positive electrode active material layer 12 and negative electrode active material layer 22 by the coatings that formed by carrier ring.Then, the example for the formation method of carrier ring 30 is described.
First, by insulating properties particle, adhesive and solvent, after adding tackifier as required, the coating that modulation carrier ring is formed.Now, carry out modulating to make the viscosity of coating to become 500mPas ~ 5000mPas.
Then, above-mentioned coating is coated on the surface of positive electrode active material layer 12 and negative electrode active material layer 22.Coating above-mentioned coating method without particular limitation of, can use ad lib from known method.Can use such as, mould is coated with the coating above-mentioned coating such as machine, gravure roll coating machine, reverse roll coater, contact roll coater, dipping roll coater, rod coater, air knife coater, Bracewell coater, brush spreader, silk screen coating machine.
Thereafter, make above-mentioned coating dry.When above-mentioned coating dry, can use from known method.Such as, the method for stipulated time, the method etc. of blowing hot-air is placed under the temperature atmosphere of regulation can be used in.Its result, forms carrier ring 30 on the surface of positive pole 10 and negative pole 20.
Fig. 4 represents an example of the lithium rechargeable battery 2 possessing electrode body 1.Lithium rechargeable battery 2, has electrode body 1 together with nonaqueous electrolytic solution 3 by the formation of accommodating in battery container 5.The impregnation electrode body at least partially 1 of nonaqueous electrolytic solution 3.
Be formed with positive pole 10 and the negative pole 20 of carrier ring 30 on surface, be formed lengthy motion picture shape.Positive pole 10 and negative pole 20, overlap in the mode of carrier ring 30 between positive pole 10 and negative pole 20, be wound into cylindrical shape.
Battery container 5, possesses the housing body 6 of bottomed cylindrical and the lid 7 of its peristome of blocking.Lid 7 and housing body 6 are all metal, mutually insulated.Lid 7 is electrically connected with positive electrode collector 11, and housing body 6 is electrically connected with negative electrode collector 21.In this lithium rechargeable battery 2, lid 7 doubles as positive terminal, and housing body 6 doubles as negative terminal.
On a face of positive pole 10, along on an edge (edge of the upside of Fig. 4) of the longitudinal direction of positive electrode collector 11, positive electrode active material layer 12 is not set and is provided with the part that positive electrode collector 11 exposes.Lid 7 is electrically connected with this exposed portion.On a face of negative pole 20, along on an edge (edge of the downside of Fig. 4) of the longitudinal direction of negative electrode collector 21, negative electrode active material layer 22 is not set and is provided with the part that negative electrode collector 21 exposes.Housing body 6 is electrically connected with this exposed portion.
Nonaqueous electrolytic solution 3, containing the lithium salts as supporting electrolyte in organic solvent (nonaqueous solvents).As lithium salts, can suitably choice for use such as, from the past as the known lithium salts that the supporting electrolyte of the nonaqueous electrolytic solution of lithium rechargeable battery uses.Such as, as this lithium salts, LiPF can be illustrated 6, LiBF 4, LiClO 4, LiAsF 6, Li (CF3SO 2) 2n, LiCF 3sO 3deng.As above-mentioned nonaqueous solvents, can the organic solvent that uses of lithium rechargeable battery that suitably choice for use is general.As particularly preferred nonaqueous solvents, the carbonates of ethylene carbonate (EC), dimethyl carbonate (DMC), methyl ethyl carbonate (EMC), diethyl carbonate (DEC), propylene carbonate (PC) etc. can be illustrated.
Lithium rechargeable battery 2, such as, manufacture as follows.First, positive pole 10 and negative pole 20 is made.Then, adopt above-mentioned method, form carrier ring 30 on the surface of positive electrode active material layer 12 and negative electrode active material layer 22.The positive pole 10 being formed with carrier ring 30 is overlapped with the negative pole 20 being formed with carrier ring 30 and is wound into cylindrical shape.Thus, electrode body 1 is formed.Thereafter, make electrode body impregnation nonaqueous electrolytic solution 3, electrode body 1 is housed in battery container 5.Lid 7 is engaged with battery container 5, sealed electrical polar body 1 and nonaqueous electrolytic solution 3.
Lithium rechargeable battery 2 of the present embodiment, can utilize as the secondary cell towards various uses.Such as, as shown in Figure 5, the power supply of the engine (motor) of the vehicle traction can carried as the vehicle 9 of automobile etc. utilizes well.The kind of vehicle 9 is without particular limitation of, typically hybrid vehicle, electric automobile, fuel cell car etc.This lithium rechargeable battery 2, can be used alone, and also can use in the mode connecting multiple battery pack in series and/or in parallel.
The present application person thinks, when forming carrier ring on the surface of negative or positive electrode (following, to be simply referred to as electrode), one of reason that the flatness as carrier ring surface reduces, has following reason.That is, by coatings to active material layer surperficial of electrode time, the solvent comprised in coating infiltrates in active material layer, and air is extruded from active material layer.This air, is formed after the drying in the film of the coating of carrier ring and passes through, and after arriving the surface of film, is discharged into outside.Now, this air can form the concavo-convex of pin hole or film surface, and the flatness of carrier ring is reduced.
The present application person also thinks, by adjusting the viscosity of coating, solvent can be suppressed the infiltration of active material layer, and then can suppress the reduction of flatness of carrier ring.The present application person, the multiple coating using viscosity different form the carrier ring that thickness is 32 μm, use laser microscope, have investigated the presence or absence of the pin hole on carrier ring surface.Its result, obtains when the viscosity of coating is lower than 500mPas, every 10mm 2produce the pin hole of about 6, when more than 500mPas, do not produce the result of pin hole.Moreover, at this said pin hole, refer to that the surface from carrier ring arrives the through trace of electrode.
As a method of the viscosity of adjustment coating, consider the amount of adjustment adhesive.The present application person, has carried out investigating the experiment how changed according to the viscosity of the amount coating of adhesive.Insulating properties particle, adhesive, solvent, employ polyethylene particles, ionomer resin, water that average grain diameter is 3 μm respectively.Experimental result is shown in Fig. 6.The transverse axis of Fig. 6, represents the weight ratio of adhesive relative to insulator particle.Can estimate relative to insulating properties particle 100 weight portion from Fig. 6, when adhesive is below 3 weight portions, the viscosity of coating becomes more than 500mPas.
In addition, as another method of the viscosity of adjustment coating, consider to add tackifier.The present application person, has carried out investigating the experiment how changed according to the viscosity of the amount coating of tackifier.Insulating properties particle, tackifier, solvent, employ polyethylene particles, Sodium Polyacrylate, water that average grain diameter is 3 μm respectively.Experimental result is shown in Fig. 7.The transverse axis of Fig. 7, represents the weight ratio of tackifier relative to insulating properties particle.Can estimate relative to insulating properties particle 100 weight portion from Fig. 7, when tackifier are more than 0.5 weight portion, the viscosity of coating becomes more than 500mPas.
< embodiment 1 >
Use average grain diameter be the polyethylene particles of 3 μm as insulating properties particle, this insulating properties particle, the ionomer resin as adhesive, the water as solvent are mixed, modulate the coating of pasty state.Mixing ratio, is set to adhesive 3 weight portion relative to insulating properties particle 100 weight portion.Determining the viscosity of above-mentioned coating, is 600mPas.Its result, when can to confirm relative to insulating properties particle 100 weight portion adhesive be below 3 weight portions, even if do not add tackifier, also can remain on more than 500mPas by the viscosity of coating.
< embodiment 2 >
Be that the polyethylene particles (insulating properties particle) of 3 μm, the ionomer resin as adhesive, the water as solvent and the Sodium Polyacrylate as tackifier mix using average grain diameter, modulate the coating of pasty state.Mixing ratio is, relative to insulating properties particle 100 weight portion, adhesive is 3 weight portions, tackifier are 0.5 weight portion.Determining the viscosity of above-mentioned coating, is 1148mPas.From with the comparing of embodiment 1, if confirm the amount increasing tackifier, then the viscosity of coating increases.
< embodiment 3 >
Mixing ratio be set to relative to insulating properties particle 100 weight portion, adhesive is 3 weight portions, and tackifier are 1 weight portion, modulate coating similarly to Example 2 in addition.Determining the viscosity of coating, is 2230mPas.From with the comparing of embodiment 1 and 2, if confirm the amount increasing tackifier, then the viscosity of coating increases.
< reference example 1 >
It is the coating of zero that tackifier, on the other hand amount of binder are added in modulation, determines its viscosity.That is, be that polyethylene particles (insulating properties particle), the water as solvent and the Sodium Polyacrylate as tackifier of 3 μm mixes using average grain diameter, modulate the coating of pasty state.Adhesive is not comprised in this coating.Mixing ratio is, is set to tackifier 0.5 weight portion relative to insulating properties particle 100 weight portion.Determining the viscosity of above-mentioned coating, is 636mPas.From the result of this result and embodiment 1, if be below 3 weight portions relative to insulating properties particle 100 parts by weight of binder, and tackifier are more than 0.5 weight portion, then more effectively the viscosity of coating can be set to more than 500mPas.
< reference example 2 >
Relative to insulating properties particle 100 weight portion, adhesive is set to 5 weight portions, tackifier are set to 1 weight portion, modulate coating similarly to Example 2 in addition.Determining the viscosity of coating, is 446mPas.From this result, when being more than 5 weight portions relative to insulating properties particle 100 parts by weight of binder, even if the addition of tackifier is set to 1 weight portion, the viscosity of coating is also lower than 500mPas.From the result of this result and embodiment 1, when amount of binder is too much, only by adding some tackifier, be difficult to the viscosity of coating to be set to more than 500mPas.
By embodiment 1 ~ 3 and reference example 1 ~ 2, at least relative to insulating properties particle 100 weight portion, when adhesive being set to below 3 weight portions and/or being set to more than 0.5 weight portion by tackifier, the viscosity of coating can be set to more than 500mPas.
From the viewpoint of the flatness of raising carrier ring, the viscosity of preferred coatings is large, and but then, few from the deviation of the coating weight making coating, make the viewpoint that painting process is stable, the viscosity of preferred coatings is not excessive.From the experience of the present application person, when the viscosity of coating is more than 5000mPas, owing to sticking with paste poor fluidity, easily cause to stick with paste in apparatus for coating and be detained.But, stick with paste the reason of being detained and becoming the deviation of coating weight, the instability of painting process can be caused.Therefore, the viscosity of preferred coatings is below 5000mPas.
< embodiment 4 >
Mixing ratio be set to relative to insulating properties particle 100 weight portion, adhesive is 5 weight portions, tackifier are 6 weight portions, has modulated coating similarly to Example 2 in addition.Determining the viscosity of coating, is 894mPas.
< embodiment 5 >
Mixing ratio be set to relative to insulating properties particle 100 weight portion, adhesive is 5 weight portions, tackifier are 12 weight portions, has modulated coating similarly to Example 2 in addition.Determining the viscosity of coating, is 1302mPas.
< embodiment 6 >
Mixing ratio be set to relative to insulating properties particle 100 weight portion, adhesive is 5 weight portions, tackifier are 22 weight portions, has modulated coating similarly to Example 2 in addition.Determining the viscosity of coating, is 1916mPas.
< embodiment 7 >
Mixing ratio be set to relative to insulating properties particle 100 weight portion, adhesive is 5 weight portions, tackifier are 44 weight portions, has modulated coating similarly to Example 2 in addition.Determining the viscosity of coating, is 3650mPas.
Fig. 8 is the figure of the result representing embodiment 4 ~ 7.From the result of embodiment 4 ~ 7, when to estimate relative to the addition of insulating properties particle 100 weight portion tackifier be below 65 weight portions, the viscosity of coating becomes below 5000mPas.
But carrier ring carries out drying to be formed by the coating being applied to the surface of the active material layer of electrode.The part by weight of dried adhesive in carrier ring, tackifier, becomes the value different respectively from the part by weight of the adhesive in coating, tackifier.The present application person, by not forming carrier ring containing the coating of tackifier, determines the weight ratio of insulating properties particle that dried carrier ring comprises and adhesive.Moisture when to be engaged in relative to insulating properties particle 100 parts by weight of binder be 3 weight portion, be insulating properties particle in the weight ratio of the solid constituent of carrier ring: adhesive=40:0.81.In this situation, the solid constituent ratio of adhesive is 2%.Therefore, when defining carrier ring with the coating containing the adhesive of below 3 weight portions relative to insulating properties particle 100 weight portion, the mass ratio of adhesive shared by carrier ring is less than 2%.
In addition, the present application person, by not forming carrier ring containing the coating of adhesive, determines the weight ratio of insulating properties particle that dried carrier ring comprises and tackifier.Moisture when to be engaged in relative to insulating properties particle 100 weight portion tackifier be 0.5 weight portion, the weight ratio of solid constituent is insulating properties particle: tackifier=40:0.1.In this situation, the solid constituent ratio of tackifier is 0.2%.In addition, moisture when to be engaged in relative to insulating properties particle 100 weight portion tackifier be 65 weight portion, the weight ratio of solid constituent is insulating properties particle: tackifier=40:11.7.In this situation, the solid constituent ratio of tackifier is 22.6%.Therefore, when utilizing the coating containing the tackifier of 0.5 weight portion ~ 65 weight portion relative to insulating properties particle 100 weight portion to define carrier ring, the mass ratio of tackifier shared by carrier ring is 0.2% ~ 22.6%.
The venting quality > of < carrier ring
The present application person, has carried out the experiment investigating the porosity of carrier ring and the relation of venting quality.Use the different insulating properties particle of average grain diameter, at thickness be the polyethylene film 40 of 10 μm surface on define the carrier ring 30 (with reference to Fig. 9) of sample 1 ~ 3.Make carrier ring 30 and polyethylene film 40 through air, measuring the time through the air of 100 milliliters, is air permeability by this timing definition.Air permeability is less, air easier through, ion permeability is higher.The results are shown in table 1.
Table 1
Make the polyethylene film of thickness 20 μm through air, determining the time through the air of 100 milliliters, is 400 seconds.The air permeability of sample 1 is 448 seconds, more about than the air permeability of polyethylene film 10%.Therefore, known sample 1 is compared with polyethylene film monomer, and ion permeability is low.On the other hand, the air permeability of sample 2 is 399 seconds, and the air permeability of sample 3 is 404 seconds, is all the level equal with polyethylene film air permeability.Therefore, known sample 2 and 3 has the ion permeability equal with polyethylene film.Per sample 2 and 3, play the ion permeability equal with the dividing plate be in the past made up of polyethylene film.The porosity of sample 1 is 12.5%, smaller.On the other hand, the porosity of sample 2 and 3 is more than 35%.It can thus be appreciated that, when the porosity of carrier ring is more than 35%, play or its above ion permeability equal with dividing plate in the past.
In addition, use other the insulating properties particle that average grain diameter is different, determine the porosity of carrier ring.The results are shown in table 2 and Figure 10.As shown in Figure 10, when the average grain diameter of insulating properties particle becomes large, porosity becomes large, and when average grain diameter is more than 3 μm, porosity becomes more than 35%.
Table 2
Above, understand the present invention in detail, but the above-described embodiment and examples only illustrate, and comprise the situation of above-mentioned concrete example having been carried out distortion, change in invention disclosed herein.

Claims (2)

1. a battery, it possesses:
Positive pole, this is just having positive electrode collector and is containing positive active material and the positive electrode active material layer formed on described positive electrode collector;
Negative pole, this negative pole has negative electrode collector and contains negative electrode active material and the negative electrode active material layer formed on described negative electrode collector; With
Containing insulating properties particle, adhesive and tackifier, and formed on the surface of at least one party of described positive electrode active material layer and described negative electrode active material layer there is insulating properties and porous carrier ring,
The mass ratio of described adhesive shared by described carrier ring is less than 2%,
The mass ratio of described tackifier shared by described carrier ring is 0.2% ~ 22.6%.
2. battery according to claim 1, the average grain diameter of described insulating properties particle is more than 3 μm, and the porosity of described carrier ring is more than 35%.
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Citations (4)

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Publication number Priority date Publication date Assignee Title
US20070009803A1 (en) * 2005-07-06 2007-01-11 Jin-Hee Kim Lithium rechargeable battery
CN1918727A (en) * 2004-02-07 2007-02-21 株式会社Lg化学 Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
WO2010074202A1 (en) * 2008-12-26 2010-07-01 日本ゼオン株式会社 Separator for lithium ion secondary battery, and lithium ion secondary battery
CN101796669A (en) * 2008-01-29 2010-08-04 日立麦克赛尔株式会社 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN1918727A (en) * 2004-02-07 2007-02-21 株式会社Lg化学 Organic/inorganic composite porous layer-coated electrode and electrochemical device comprising the same
US20070009803A1 (en) * 2005-07-06 2007-01-11 Jin-Hee Kim Lithium rechargeable battery
CN101796669A (en) * 2008-01-29 2010-08-04 日立麦克赛尔株式会社 Slurry for forming insulating layer, separator for electrochemical device, method for producing the same, and electrochemical device
WO2010074202A1 (en) * 2008-12-26 2010-07-01 日本ゼオン株式会社 Separator for lithium ion secondary battery, and lithium ion secondary battery

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